JP3866370B2 - Polyurethane prepolymers having alkoxysilane groups and hydantoin groups and their use in the production of sealants - Google Patents

Polyurethane prepolymers having alkoxysilane groups and hydantoin groups and their use in the production of sealants Download PDF

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JP3866370B2
JP3866370B2 JP13743597A JP13743597A JP3866370B2 JP 3866370 B2 JP3866370 B2 JP 3866370B2 JP 13743597 A JP13743597 A JP 13743597A JP 13743597 A JP13743597 A JP 13743597A JP 3866370 B2 JP3866370 B2 JP 3866370B2
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nco
prepolymer
alkoxysilane
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JPH1053637A (en
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ルツツ・シユマールステイーク
ライナー・レツテイグ
ゲツツ・リムベツク
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Alkoxysilane- and hydantoin groups exhibiting polyurethane prepolymers of formula (I) are new, where A = group formed by removal of the NCO- groups from an isocyanate prepolymer with an NCO-content of 0.4-5% and an average functionality of 1.5-4; R = 1-8C alkyl group; and X, Y, Z = 1-4C alkyl- or alkoxy group, provided that at least one of the groups is an alkoxy group. In (I), A = a group which is formed by removal of the NCO-groups from an isocyanate prepolymer based on polyether polyols with an average functionality of 1.8-2.2 and an NCO-content of 0.5-2%; R = 1-2C alkyl group; and X, Y, Z = methoxy- or ethoxy groups.

Description

【０００１】
【発明の属する技術分野】
本発明は、アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマー、その製造方法、およびポリウレタンシーラント組成物の結合剤としてのその使用に関する。
【０００２】
【従来の技術】
シランの重縮合を介して架橋するアルコキシシラン官能性ポリウレタンが公知である（例えば「アドヘッシブ・エイジ（adhesives Age ) 」4 /1995 、p30 ff.,参照）。アルコキシシランを末端基とする湿分硬化一成分ポリウレタンは、建築および自動車産業で、軟質の塗料および封止剤、ならびに接着剤としてますます使用されている。これらの適用の際には、伸び、接着力および硬化速度に関する厳しい条件が要求される。最近入手できる方式でも特に、自動車産業が要求する特性レベルを全て、達成することはできない。
【０００３】
Ｎ−アリールアミノシランをＮＣＯ−プレポリマーとを反応させることにより得られるアルコキシシラン−官能性ポリウレタンが、EP-A676403から公知である。これらの化合物は、自動車産業の要求、例えば機械特性に関しては満足する。しかし、架橋重合体の熱的安定性の欠如が製品の問題となる。この欠陥の理由は、置換（特にアリール基で置換）された尿素に知られている熱的不安定性にある。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、良好な伸びおよび接着力とともに、良好な熱的安定性を有するアルコキシシラン官能性ポリウレタンを提供することにある。
この目的は、以下に詳細に記載するこの発明のポリウレタンプレポリマーにより達成される。
【０００５】
【課題を解決するための手段】
本発明は、式(I) ：
【化３】

Figure 0003866370
（ここで、Ａは、ＮＣＯ含有量を０．４〜５％有するイソシアネートプレポリマーからＮＣＯ基を除いて得られる基を示し、Ｒは、線状または分岐状の炭素原子数１〜８のアルキル基を示し、Ｘ、ＹおよびＺは、同一または異なり、炭素原子数１〜４のアルキルまたはアルコキシ基であって、かつ少なくとも１個の基はアルコキシ基であり、ｎは平均値で１．５〜４である）
に相当する、アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマーに関する。
この発明は、また、アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマーの製造方法、およびシーラントの製造へのその使用に関する。
【０００６】
【発明の実施の形態】
本発明のアルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマーは、
ａ）イソシアネートプレプレポリマーの全ＮＣＯ基と、例えばEP-A596360に記載されたようなアルコキシシラン基およびアミノ基を有する化合物との反応（米国特許5,364,955 、ここでは参照のために引用）、ならびに
ｂ）それに続く縮合環化反応
による二段階工程で製造される。
この発明で製造された生成物は、機械的特性が改良され、表面粘着性が減少する。
【０００７】
本発明に従い使用されるイソシアネートプレポリマーは公知である。それらは、ジイソシアネートと、エーテル、エステルおよび／またはカーボネート基を有する高分子量のポリヒドロキシル化合物、場合により少量の低分子量ポリヒドロキシル化合物の混合物とを反応させることにより製造される。適するＮＣＯプレポリマーは、ＮＣＯ基を０．４〜５％、好ましくは０．５〜２％有し、かつ平均官能価（「ｎ」で表す）が１．５〜４、好ましくは１．７〜３、さらに好ましくは１．８〜２．２である。
【０００８】
適するジイソシアネートは、脂肪族、脂環式および／または芳香族ジイソシアネートから選ばれる。好ましくは、芳香族もしくは脂環式ジイソシアネート、またはこれらの混合物である。「芳香族」および／または「脂環式」ジイソシアネートは、１分子あたり少なくとも１個の芳香族および／または脂環式の環を有するものを意味し、ここで好ましくは、二個のイソシアネート基の少なくとも一個は、芳香族および／または脂環式の環に直接結合する。
【０００９】
適するジイソシアネートＡ）の例としては、分子量が１７４〜３００の芳香族または脂環式ジイソシアネート、例えば２，４−ジイソシアナトトルエン（および、これと好ましくは混合物に基づき３５重量％までの２，６−ジイソシアナトトルエンとの混合物）；４，４’−ジフェニルメタンジイソシアネート（およびこれと、２，４’−ジフェニルメタンジイソシアネートおよび／または２，２’−ジフェニルメタンジイソシアネートとの混合物）、ビス−（４−イソシアナトシクロヘキシル）メタン、１−イソシアナト−３，３，５−トリメチル−５−イソシアナトメチルシクロヘキサン（ＩＰＤＩ）、１−イソシアナト−１−メチル−４（３）−イソシアナトメチルシクロヘキサン、および１，３−ジイソシアナト−６−メチルシクロヘキサン（および、これと１，３−ジイソシアネト−２−メチルシクロヘキサンとの混合物）が挙げられる。これらのジイソシアネートの混合物もまた使用することができる。
【００１０】
イソシアネートプレポリマーの製造に適する高分子量ポリヒドロキシル化合物は、１分子あたり平均して１．５〜４個のヒドロキシル基を有し、かつ数平均分子量（ヒドロキシル官能価およびヒドロキシル基含有量から換算）が５００〜１０，０００、好ましくは１８００〜８０００のものである。
【００１１】
適する高分子量ポリヒドロキシル化合物の例としては、低分子量アルコール、ならびにアジピン酸、セバシン酸、フタール酸、イソフタール酸、テトラヒドロフタール酸、ヘキサヒドロフタール酸、マレイン酸、これらの無水物およびこれらの混合物および／または酸無水物のような多塩基性カルボン酸から調製されるポリオールが挙げられる。ヒドロキシル基を有するポリラクトン類（特にポリ−ε−カプロラクトン）も、該プレポリマーの製造に好適である。
【００１２】
プレポリマーの製造に適する形態は、ポリエーテルポリオールであり、これは適当な出発分子をアルコキシル化する公知の方法で得られる。適当な出発分子は、ポリオール、水、少なくとも二個のＮ−Ｈ結合を有する有機ポリアミンおよびこれらの混合物が挙げられる。アルコキシル化反応に適するアルケンオキサイドは、好ましくはエチレンオキサイドおよび／またはプロピレンオキサイドであり、これらは連続的にまたは混和物で用いられる。
【００１３】
他の適当なポリオールには、ヒドロキシル基を有するポリカーボネートが挙げられ、これはジオールと、ホスゲンまたはジフェニルカーボネートのようなジアリールカーボネートとの反応により製造される。
ポリヒドロキシル化合物の混合物も、ＮＣＯプレポリマーの製造に好適である。好ましくは、専らポリエーテルポリオールが使われる。
ＮＣＯプレポリマーの製造に、必要に応じて分子量が３２〜５００以下の低分子量モノ〜ヘキサヒドリックアルコールを使用してよい。例には、モノまたはポリヒドリックアルカノール、例えばメタノール、エタノール、ｎ−ヘキサノール、２−エチルヘキサノール、エチレングリコール、ポリプレングリコール、グリセロール、トリメチロールプロパン、ペンタエリトリトール、ソルビトール、アミノアルコール類（例えばエタノールアミンまたはＮ，Ｎ−ジメチルエタノールアミン）およびジエチレングリコールが挙げられる。ｔｅｒｔ−窒素原子を有するアミノアルコール類（例えば、Ｎ，Ｎ−ジメチルエタノールアミン）が、成分ｂ）中に在って使われるときは、触媒として機能する窒素原子は同時に結合剤中に組み込まれる。
【００１４】
該ＮＣＯプレポリマーは、ジイソシアネートおよびポリオール成分を、４０〜１２０℃、好ましくは５０〜１００℃の温度で、ＮＣＯ／ＯＨ当量比が１．３：１〜２０：１、好ましくは１．４：１〜１０：１で反応させることにより製造される。イソシアネートプレポリマーの製造中にウレタン基を介した鎖延長を望む場合、ＮＣＯ／ＯＨ当量比は１．３：１〜２：１を選ぶ。鎖延長を望まない場合、過剰量のジイソシアネートが好ましく、それはＮＣＯ／ＯＨ当量比４：１〜２０：１、好ましくは５：１〜１０：１に相当する。過剰量のジイソシアネートは、反応が終了したとき薄層蒸留により除去される。
アミンまたは有機金属触媒のような公知触媒を、必要に応じてプレポリマーの製造に使用してよい。
【００１５】
本発明の方法の第一段階では、該ＮＣＯプレポリマーは、式(II)
【化４】
Figure 0003866370
（ここで、ＲおよびＲ1 は同一または異なり、炭素原子数１〜８、好ましくは炭素原子数１〜４、より好ましくは１〜２のアルキル基を示し、Ｘ、ＹおよびＺは同一または異なり、炭素原子数１〜４のアルキル基またはアルコキシ基、かつ少なくとも一個、好ましくは３個全ての基がアルコキシ基である）
に相当する、アルコキシシラン基およびアミノ基を含有する化合物と反応する。
【００１６】
アルコキシシラン基およびアミノ基を含有する化合物は、例えばEP-A596,360 （米国特許5,364,955 、ここに参照のために引用）に記載されるように、式(III)
【化５】
Figure 0003866370
に相当するアミノアルキルアルコキシシランと、式(IV)
【化６】
ＲＯＯＣ−ＣＨ＝ＣＨ−ＣＯＯＲ′ （IV）
に相当するマレイン酸および／またはフマール酸エステルとを反応させることにより得られる。
【００１７】
適するアミノアルキルアルコキシシランには、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、および３−アミノプロピル−メチル−ジエトキシシランが挙げられる。３−アミノプロピルトリメトキシシランおよび３−アミノプロピルトリエトキシシランが好ましい。
【００１８】
該ＮＣＯプレポリマーを、アルコキシシラン基およびアミノ基を含有する化合物と、０〜６０℃、好ましくは２０〜５０℃で反応させる。使用するＮＣＯ基１モルあたり０．９５〜１．１モルのアミノシリル化合物を使用する、好ましくは、使用するＮＣＯ基１モルあたりアミノシリル化合物１モルを使用する。
【００１９】
イソシアネート基とアミン基との反応後に得られるプレポリマーは、本質的にイソシアネート基を持たず、本発明の第二段階の、例えば米国特許３，５４９，５９９に記載されるような縮合反応で環化する。
環化のためには、置換尿素基を有するプレポリマーを、５０〜１２０℃、好ましくは８０〜１２０℃の温度で加熱する。ここで、モノアルコールＲ−ＯＨおよび／またはＲ’−ＯＨが生成する。必要に応じて酸性または塩基性触媒により、環化縮合反応を促進させる。所望なら、生成するモノアルコールを反応混合物から蒸留により除いてもよい。しかし、アルコールを反応混合物内に残すことが望ましい。
【００２０】
本発明のアルコキシシラン基およびヒダントイン基を有するプレポリマーは、イソシアネートフリーのポリウレタンシーラントの製造のために重要な結合剤であり、このポリウレタンシーラントは大気中の水分の存在下でシランポリ縮合により架橋する。
これらのシーラントを製造するために、アルコキシシラン基およびヒダントイン基を有するプレポリマーは、シーラントの製造に公知の方法に従い、必要に応じて添加剤、例えば可塑剤、充填剤、顔料、補助剤、チクソトロピー剤、触媒を混合してよい。
架橋重合体は、優れたゴム状弾性、低い表面粘着性および顕著な温度安定性の特徴を示す。
【００２１】
以下の実施例では、部および％はすべて重量である。粘度はＤＩＮ５３０１９に従い、回転粘度計を用いて２３℃で測定した。
【実施例】
【００２２】
実施例１
２０００ｇのポリエーテルジオール（ＯＨ価２８を有し、プロピレングリコールをプロポキシ化（ｐｒｏｐｏｘｉｌａｔｉｏｎ）し、次いで該プロポキシ化された化合物のエトキシ化により製造され、ＰＯ／ＥＯ比＝８０：２０である）を、１５５ｇのイソホロンジイソシアネートとを、１００℃で，理論ＮＣＯ含有量が０．７８％になるまで反応させた。４０℃に冷却後、１４０．４ｇのＮ−（３−トリメトキシ−シリルプロピル）アスパラギン酸ジエチルエステル（EP-A596,360 の実施例５、米国特許5,364,955 に従って製造、ここに参考のために引用）を定常的に添加し、ＩＲスペクトルでイソシアナート基のバンドが検出されなくなるまで攪拌を続けた。次いで、１００℃に加熱することにより環化縮合反応を開始し、生成したエタノールを減圧下で留去した（約１８ｇ）。得られた生成物は、粘度が５４，０００ｍＰａ．ｓ（２３℃）であった。
薄膜をガラス上に流し、ジブチル錫ジアセテートを使用した触媒作用の下、一晩かけて硬化させ、透明でショアーＡ硬度が２０の高軟質プラスチックを得た。
【００２３】
実施例２
１０００ｇのポリエーテルジオール（ＯＨ価５６を有し、プロピレングリコールのプロポキシ化により製造）と、１２２ｇの２，４−ジイソシアナトトルエンとを、６０℃で、理論ＮＣＯ含有量が１．５％になるまで反応させた。４０℃に冷却後、１４６ｇのＮ−（３−トリメトキシシリルプロピル）アスパラギン酸ジエチルエステル（EP-A596,360 の実施例２、米国特許5,364,955 に従って製造、ここに参考のために引用）を定常的に添加し、ＩＲスペクトルでイソシアナート基のバンドが検出されなくなるまで攪拌を続けた。次いで、１００℃に加熱することにより環化縮合反応を開始し、メタノールを合計１２ｇを減圧下で留去した。得られた生成物は、粘度が６９，０００ｍＰａ．ｓ（２３℃）であった。
ガラス上に流した薄膜を、ジブチル錫ジアセテートを用いた触媒作用の下、２４時間かけて硬化させ、透明でショアーＡ硬度が２８の軟質プラスチックを得た。
【００２４】
実施例３
実施例１で得たポリエーテルジオール２０００ｇと、７７．７ｇのイソホロンジイソシアネートおよび９１．７ｇのジシクロヘキシルメタンジイソシアネートとを、１００℃で、理論ＮＣＯ含有量が０．７５％になるまで反応させた。４０℃に冷却後、１４０．４ｇのＮ−（３−トリメトキシ−シリルプロピル）アスパラギン酸ジメチルエステル（EP-A596,360 の実施例４、米国特許5,364,955 に従って製造、ここに参考のために引用）を定常的に添加し、ＩＲスペクトルでイソシアナート基のバンドが検出されなくなるまで攪拌を続けた。２５７ｇの汎用市販の可塑剤〔メサモル（Mesamoll) 、バイエル・エージー〕で希釈後、１００℃に加熱することにより環化縮合反応を開始した。ＩＲスペクトル分析の１６５０ｃｍ-1のバンド消失により反応を追跡し、６時間後に終了した。得られた生成物は、粘度が２８，０００ｍＰａ．ｓ（２３℃）であった。
ガラス板へに塗布した薄膜を、ジブチル錫ジアセテートを用いた触媒作用の下、一晩かけて硬化させ、透明でショアーＡ硬度が２３の高軟質プラスチックを形成した。
【００２５】
例４
EP-A596,360 （米国特許5,364,955 ）の実施例４に従った、本発明に従わない比較例
環化縮合反応を省いた以外は、実施例１を繰り返した。得られた生成物は、粘度が５９，０００ｍＰａ．ｓ（２３℃）であった。
ガラス板上へ流した薄膜を、ジブチル錫ジアセテートを用いた触媒作用の下、一晩かけて硬化させ、ショアーＡ硬度が１７の透明なプラスチックを形成した。この薄膜は、表面粘着性が残留し、伸びは、実施例１の薄膜に比べてかなり低かった。
【００２６】
実施例５−イソシアネートフリーポリウレタンシーラントの製造
汎用市販のプラネタリーミキサー内で以下の成分を加工し、シーラントを形成した：
実施例１の反応生成物 ３３重量部、
白亜 ３７重量部、
二酸化チタン ６重量部、
可塑剤 １６重量部、
（ユニモール（Unimoll) BB、バイエル・エージー）
水化ひまし油 ７重量部、
ジブチル錫アセテート １重量部。
得られたシーラントは、優れた安定性を有し、実質的にすべての基体に接着し、皮膜(skin)形成時間が約５時間で硬化した。
【００２７】
硬化したシーラントの以下の機械特性を測定した：
硬度 ショアーＡ ２１
引裂強さ １．１Ｎ／ｍｍ2
１００％モジュラス ０．３Ｎ／ｍｍ2
破断伸び ５８０％
引裂強さ抵抗 ２．５Ｎ／ｍｍ
【００２８】
以上、本発明を例示の目的で詳細に説明したが、これは単に例示のためであり、特許請求の範囲により限定されるものを除き、当業者により本発明の精神および範囲から離れることなく変更がなされると解されるべきである。
【００２９】
本発明の実施態様は、例えば以下のとおりである。
１．式(I) ：
【化７】
Figure 0003866370
（ここで、Ａは、ＮＣＯ含有量を０．４〜５％有するイソシアネートプレポリマーからＮＣＯ基を除いて得られる基を示し、Ｒは、線状または分岐状の炭素原子数１〜８のアルキル基を示し、Ｘ、ＹおよびＺは、同一または異なり、炭素原子数１〜４のアルキルまたはアルコキシ基であって、かつ少なくとも１個の基はアルコキシ基であり、ｎは平均値で１．５〜４である）
に相当する、アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマー。
【００３０】
２．前記イソシアネートプレポリマーが、ポリエーテルポリオールをベースとする、上記第１項のポリウレタンプレポリマー。
３．ｎが、平均値で１．８〜２．２である、上記第１項のポリウレタンプレポリマー。
４．ｎが、平均値で１．８〜２．２である、上記第２項のポリウレタンプレポリマー。
５．前記イソシアネートプレポリマーは、ＮＣＯ含有量が０．５〜２％である、上記第１項のポリウレタンプレポリマー。
６．前記イソシアネートプレポリマーは、ＮＣＯ含有量が０．５〜２％である、上記第２項のポリウレタンプレポリマー。
７．Ｒが、炭素原子を１または２個有するアルキル基を示す、上記第１項のポリウレタンプレポリマー。
８．Ｒが、炭素原子を１または２個有するアルキル基を示す、上記第２項のポリウレタンプレポリマー。
９．Ｒが、炭素原子を１または２個有するアルキル基を示す、上記第３項のポリウレタンプレポリマー。
【００３１】
10．Ｒが、炭素原子を１または２個有するアルキル基を示す、上記第６項のポリウレタンプレポリマー。
11. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第１項のポリウレタンプレポリマー。
12. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第２項のポリウレタンプレポリマー。
13. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第４項のポリウレタンプレポリマー。
14. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第６項のポリウレタンプレポリマー。
15. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第７項のポリウレタンプレポリマー。
16. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第８項のポリウレタンプレポリマー。
17. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第９項のポリウレタンプレポリマー。
18. Ｘ、ＹおよびＺが、同一または異なり、メトキシ基またはエトキシ基を示す、上記第10項のポリウレタンプレポリマー。
【００３２】
19．アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマーの製造方法であって、
i)ＮＣＯ基含有量を０．４〜５％有し、平均官能価が１．５〜４のイソシアネートプレポリマー基と
ｉi)式(II)：
【化８】
Figure 0003866370
（ここで、Ｒは線状または分岐状の炭素原子数１〜８アルキル基を示し、Ｘ、ＹおよびＺは同一または異なり、アルキルまたはアルコキシ基であり、かつ少なくとも一個の基はアルコキシ基である）
に相当するアミノアルコキシシランと反応させ、
次いで、５０〜１６０℃で環化縮合によりヒダントイン基を形成することからなる該製造方法。
20．上記第１項のポリウレタンプレポリマーを含有する湿分硬化性組成物。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to polyurethane prepolymers having alkoxysilane groups and hydantoin groups, to a process for their preparation and to their use as binders in polyurethane sealant compositions.
[0002]
[Prior art]
Alkoxysilane functional polyurethanes that crosslink via polycondensation of silanes are known (see, for example, “Adhesive Ages” 4/1995, p30 ff.). Moisture-cure one-component polyurethanes based on alkoxysilanes are increasingly being used as soft paints and sealants and adhesives in the construction and automotive industries. These applications require stringent conditions regarding elongation, adhesion and cure speed. Even with the recently available schemes, not all the characteristic levels required by the automotive industry can be achieved.
[0003]
An alkoxysilane-functional polyurethane obtained by reacting N-arylaminosilane with an NCO-prepolymer is known from EP-A676403. These compounds satisfy the requirements of the automotive industry, for example with respect to mechanical properties. However, the lack of thermal stability of the crosslinked polymer is a product problem. The reason for this deficiency is the thermal instability known to substituted ureas (particularly substituted with aryl groups).
[0004]
[Problems to be solved by the invention]
It is an object of the present invention to provide an alkoxysilane functional polyurethane having good thermal stability as well as good elongation and adhesion.
This object is achieved by the polyurethane prepolymer of the present invention described in detail below.
[0005]
[Means for Solving the Problems]
The present invention relates to a compound of formula (I):
[Chemical 3]
Figure 0003866370
(Here, A represents a group obtained by removing an NCO group from an isocyanate prepolymer having an NCO content of 0.4 to 5%, and R represents a linear or branched alkyl having 1 to 8 carbon atoms. X, Y and Z are the same or different and are an alkyl or alkoxy group having 1 to 4 carbon atoms, and at least one group is an alkoxy group, and n is an average value of 1.5 ~ 4)
And a polyurethane prepolymer having an alkoxysilane group and a hydantoin group.
The invention also relates to a process for the production of polyurethane prepolymers having alkoxysilane groups and hydantoin groups, and their use in the production of sealants.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The polyurethane prepolymer having an alkoxysilane group and a hydantoin group of the present invention is
a) reaction of all NCO groups of the isocyanate pre-prepolymer with compounds having alkoxysilane groups and amino groups as described, for example, in EP-A 596 360 (US Pat. No. 5,364,955, hereby incorporated by reference), and b) Produced in a two-step process by a subsequent condensed cyclization reaction.
The product produced in this invention has improved mechanical properties and reduced surface tack.
[0007]
The isocyanate prepolymers used in accordance with the present invention are known. They are prepared by reacting diisocyanates with a mixture of high molecular weight polyhydroxyl compounds having ether, ester and / or carbonate groups, optionally with small amounts of low molecular weight polyhydroxyl compounds. Suitable NCO prepolymers have an NCO group of 0.4-5%, preferably 0.5-2% and an average functionality (denoted "n") of 1.5-4, preferably 1.7. To 3, more preferably 1.8 to 2.2.
[0008]
Suitable diisocyanates are selected from aliphatic, alicyclic and / or aromatic diisocyanates. Preference is given to aromatic or alicyclic diisocyanates or mixtures thereof. “Aromatic” and / or “cycloaliphatic” diisocyanates mean those having at least one aromatic and / or cycloaliphatic ring per molecule, preferably here of two isocyanate groups At least one is bonded directly to the aromatic and / or alicyclic ring.
[0009]
Examples of suitable diisocyanates A) are aromatic or cycloaliphatic diisocyanates with a molecular weight of 174 to 300, for example 2,4-diisocyanatotoluene (and preferably up to 35% by weight of 2,6 based on the mixture). A mixture with diisocyanatotoluene); 4,4′-diphenylmethane diisocyanate (and a mixture thereof with 2,4′-diphenylmethane diisocyanate and / or 2,2′-diphenylmethane diisocyanate), bis- (4-isocyanate) Natocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl-4 (3) -isocyanatomethylcyclohexane, and 1,3- Diisocyanato-6-methylcyclohex Down (and mixtures of this with 1,3 Jiisoshianeto-2-methyl cyclohexane) and the like. Mixtures of these diisocyanates can also be used.
[0010]
High molecular weight polyhydroxyl compounds suitable for the production of isocyanate prepolymers have an average of 1.5 to 4 hydroxyl groups per molecule and have a number average molecular weight (converted from hydroxyl functionality and hydroxyl group content). 500 to 10,000, preferably 1800 to 8000.
[0011]
Examples of suitable high molecular weight polyhydroxyl compounds include low molecular weight alcohols, as well as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, their anhydrides and mixtures thereof And / or polyols prepared from polybasic carboxylic acids such as acid anhydrides. Polylactones having hydroxyl groups (especially poly-ε-caprolactone) are also suitable for producing the prepolymer.
[0012]
A suitable form for the preparation of the prepolymer is a polyether polyol, which can be obtained by known methods of alkoxylating suitable starting molecules. Suitable starting molecules include polyols, water, organic polyamines having at least two NH bonds, and mixtures thereof. Suitable alkene oxides for the alkoxylation reaction are preferably ethylene oxide and / or propylene oxide, which are used continuously or in admixture.
[0013]
Other suitable polyols include polycarbonates having hydroxyl groups, which are prepared by reaction of diols with diaryl carbonates such as phosgene or diphenyl carbonate.
Mixtures of polyhydroxyl compounds are also suitable for the production of NCO prepolymers. Preferably, exclusively polyether polyols are used.
For the production of the NCO prepolymer, a low molecular weight mono-hexahydric alcohol having a molecular weight of 32 to 500 or less may be used as necessary. Examples include mono- or polyhydric alkanols such as methanol, ethanol, n-hexanol, 2-ethylhexanol, ethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, amino alcohols (eg ethanolamine) Or N, N-dimethylethanolamine) and diethylene glycol. When amino alcohols having a tert-nitrogen atom (eg N, N-dimethylethanolamine) are used in component b), the nitrogen atom that functions as a catalyst is simultaneously incorporated into the binder.
[0014]
The NCO prepolymer comprises a diisocyanate and a polyol component at a temperature of 40 to 120 ° C., preferably 50 to 100 ° C., and an NCO / OH equivalent ratio of 1.3: 1 to 20: 1, preferably 1.4: 1. It is produced by reacting at 10: 1. If chain extension via urethane groups is desired during the preparation of the isocyanate prepolymer, the NCO / OH equivalent ratio is selected from 1.3: 1 to 2: 1. If chain extension is not desired, an excess of diisocyanate is preferred, which corresponds to an NCO / OH equivalent ratio of 4: 1 to 20: 1, preferably 5: 1 to 10: 1. Excess diisocyanate is removed by thin layer distillation when the reaction is complete.
Known catalysts such as amines or organometallic catalysts may be used in the preparation of the prepolymer if desired.
[0015]
In the first stage of the process of the invention, the NCO prepolymer is of the formula (II)
[Formula 4]
Figure 0003866370
(Wherein R and R 1 are the same or different and each represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and X, Y and Z are the same or different. , An alkyl group having 1 to 4 carbon atoms or an alkoxy group, and at least one, preferably all three groups are alkoxy groups)
It reacts with a compound containing an alkoxysilane group and an amino group.
[0016]
Compounds containing an alkoxysilane group and an amino group may be represented by the formula (III) as described, for example, in EP-A596,360 (US Pat. No. 5,364,955, incorporated herein by reference).
[Chemical formula 5]
Figure 0003866370
An aminoalkylalkoxysilane corresponding to the formula (IV)
[Chemical 6]
ROOC-CH = CH-COOR '(IV)
It is obtained by reacting maleic acid and / or fumaric acid ester corresponding to
[0017]
Suitable aminoalkylalkoxysilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyl-methyl-diethoxysilane. 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferred.
[0018]
The NCO prepolymer is reacted with a compound containing an alkoxysilane group and an amino group at 0 to 60 ° C., preferably 20 to 50 ° C. 0.95 to 1.1 moles of aminosilyl compound are used per mole of NCO group used, preferably 1 mole of aminosilyl compound is used per mole of NCO group used.
[0019]
The prepolymer obtained after the reaction of the isocyanate group with the amine group is essentially free of isocyanate groups and is subjected to a ring reaction in a condensation reaction as described in the second stage of the invention, eg, US Pat. No. 3,549,599. Turn into.
For the cyclization, the prepolymer having substituted urea groups is heated at a temperature of 50 to 120 ° C., preferably 80 to 120 ° C. Here, monoalcohol R—OH and / or R′—OH is produced. The cyclization condensation reaction is promoted with an acidic or basic catalyst as necessary. If desired, the resulting monoalcohol may be removed from the reaction mixture by distillation. However, it is desirable to leave the alcohol in the reaction mixture.
[0020]
The prepolymers having alkoxysilane groups and hydantoin groups of the present invention are important binders for the production of isocyanate-free polyurethane sealants, which are crosslinked by silane polycondensation in the presence of atmospheric moisture.
In order to produce these sealants, prepolymers having alkoxysilane groups and hydantoin groups are prepared according to known methods for the production of sealants and optionally with additives such as plasticizers, fillers, pigments, adjuvants, thixotropies. An agent and a catalyst may be mixed.
Cross-linked polymers exhibit excellent rubbery elasticity, low surface tack and remarkable temperature stability characteristics.
[0021]
In the following examples, all parts and percentages are by weight. The viscosity was measured at 23 ° C. using a rotational viscometer in accordance with DIN 53019.
【Example】
[0022]
Example 1
2000 g of polyether diol (having an OH number of 28, produced by propoxylation of propylene glycol and then ethoxylation of the propoxylated compound, PO / EO ratio = 80: 20) 155 g of isophorone diisocyanate was reacted at 100 ° C. until the theoretical NCO content was 0.78%. After cooling to 40 ° C., 140.4 g of N- (3-trimethoxy-silylpropyl) aspartic acid diethyl ester (prepared according to Example 5 of EP-A596,360, US Pat. No. 5,364,955, incorporated herein by reference) The mixture was constantly added, and stirring was continued until no isocyanate group band was detected in the IR spectrum. Subsequently, the cyclocondensation reaction was started by heating to 100 ° C., and the produced ethanol was distilled off under reduced pressure (about 18 g). The resulting product has a viscosity of 54,000 mPa.s. s (23 ° C.).
The thin film was cast on glass and cured overnight under catalytic action using dibutyltin diacetate to obtain a transparent, high soft plastic with a Shore A hardness of 20.
[0023]
Example 2
1000 g of polyether diol (having an OH number of 56 and produced by propoxylation of propylene glycol) and 122 g of 2,4-diisocyanatotoluene at 60 ° C. with a theoretical NCO content of 1.5% The reaction was continued until After cooling to 40 ° C., 146 g of N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester (prepared according to EP-A596,360, Example 2, US Pat. No. 5,364,955, incorporated herein by reference) The stirring was continued until no isocyanate group band was detected in the IR spectrum. Subsequently, the cyclization condensation reaction was started by heating to 100 ° C., and a total of 12 g of methanol was distilled off under reduced pressure. The resulting product has a viscosity of 69,000 mPa.s. s (23 ° C.).
The thin film cast on the glass was cured for 24 hours under the catalytic action using dibutyltin diacetate to obtain a transparent soft plastic having a Shore A hardness of 28.
[0024]
Example 3
2000 g of the polyether diol obtained in Example 1 was reacted with 77.7 g of isophorone diisocyanate and 91.7 g of dicyclohexylmethane diisocyanate at 100 ° C. until the theoretical NCO content was 0.75%. After cooling to 40 ° C., 140.4 g of N- (3-trimethoxy-silylpropyl) aspartic acid dimethyl ester (prepared according to EP-A596,360, Example 4, US Pat. No. 5,364,955, incorporated herein by reference) The mixture was constantly added, and stirring was continued until no isocyanate group band was detected in the IR spectrum. After diluting with 257 g of a general-purpose commercially available plasticizer (Mesamoll, Bayer AG), the cyclization condensation reaction was started by heating to 100 ° C. The reaction was followed by the disappearance of the 1650 cm −1 band in IR spectral analysis and was complete after 6 hours. The resulting product has a viscosity of 28,000 mPa.s. s (23 ° C.).
The thin film coated on the glass plate was cured overnight under a catalytic action using dibutyltin diacetate to form a transparent and highly flexible plastic having a Shore A hardness of 23.
[0025]
Example 4
Example 1 was repeated, except that the comparative cyclization condensation reaction according to Example 4 of EP-A 596,360 (US Pat. No. 5,364,955) and not according to the invention was omitted. The resulting product has a viscosity of 59,000 mPa.s. s (23 ° C.).
The thin film cast on the glass plate was cured overnight under the catalytic action using dibutyltin diacetate to form a transparent plastic having a Shore A hardness of 17. This thin film remained surface sticky, and its elongation was considerably lower than that of the thin film of Example 1.
[0026]
Example 5-Preparation of Isocyanate Free Polyurethane Sealant The following ingredients were processed in a commercially available planetary mixer to form a sealant:
33 parts by weight of the reaction product of Example 1
37 parts by weight of chalk,
6 parts by weight of titanium dioxide,
16 parts by weight of plasticizer,
(Unimoll BB, Bayer AG)
7 parts by weight of hydrated castor oil,
1 part by weight of dibutyltin acetate.
The resulting sealant had excellent stability, adhered to virtually all substrates, and cured with a skin formation time of about 5 hours.
[0027]
The following mechanical properties of the cured sealant were measured:
Hardness Shore A 21
Tear strength 1.1 N / mm 2
100% modulus 0.3 N / mm 2
Elongation at break 580%
Tear strength resistance 2.5N / mm
[0028]
Although the present invention has been described in detail for purposes of illustration, this is for purposes of illustration only and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention, except as limited by the appended claims. It should be understood that is done.
[0029]
Embodiments of the present invention are as follows, for example.
1. Formula (I):
[Chemical 7]
Figure 0003866370
(Here, A represents a group obtained by removing an NCO group from an isocyanate prepolymer having an NCO content of 0.4 to 5%, and R represents a linear or branched alkyl having 1 to 8 carbon atoms. X, Y and Z are the same or different and are an alkyl or alkoxy group having 1 to 4 carbon atoms, and at least one group is an alkoxy group, and n is an average value of 1.5 ~ 4)
A polyurethane prepolymer having an alkoxysilane group and a hydantoin group.
[0030]
2. The polyurethane prepolymer of claim 1, wherein the isocyanate prepolymer is based on a polyether polyol.
3. The polyurethane prepolymer according to item 1, wherein n is 1.8 to 2.2 on average.
4). 3. The polyurethane prepolymer of the second item, wherein n is an average value of 1.8 to 2.2.
5). The polyurethane prepolymer according to item 1, wherein the isocyanate prepolymer has an NCO content of 0.5 to 2%.
6). The polyurethane prepolymer according to item 2, wherein the isocyanate prepolymer has an NCO content of 0.5 to 2%.
7). The polyurethane prepolymer of item 1 above, wherein R represents an alkyl group having 1 or 2 carbon atoms.
8). The polyurethane prepolymer of item 2, wherein R represents an alkyl group having 1 or 2 carbon atoms.
9. The polyurethane prepolymer of item 3, wherein R represents an alkyl group having 1 or 2 carbon atoms.
[0031]
Ten. The polyurethane prepolymer of item 6, wherein R represents an alkyl group having 1 or 2 carbon atoms.
11. The polyurethane prepolymer of item 1, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
12. The polyurethane prepolymer of item 2 above, wherein X, Y and Z are the same or different and represent a methoxy group or an ethoxy group.
13. The polyurethane prepolymer of item 4, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
14. The polyurethane prepolymer of item 6 above, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
15. The polyurethane prepolymer of item 7, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
16. The polyurethane prepolymer of item 8 above, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
17. The polyurethane prepolymer of item 9, wherein X, Y and Z are the same or different and each represents a methoxy group or an ethoxy group.
18. The polyurethane prepolymer of claim 10, wherein X, Y and Z are the same or different and represent a methoxy group or an ethoxy group.
[0032]
19. A method for producing a polyurethane prepolymer having an alkoxysilane group and a hydantoin group,
i) an isocyanate prepolymer group having an NCO group content of 0.4 to 5% and an average functionality of 1.5 to 4 and ii) Formula (II):
[Chemical 8]
Figure 0003866370
(Wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms, X, Y and Z are the same or different, and are an alkyl or alkoxy group, and at least one group is an alkoxy group. )
With an aminoalkoxysilane corresponding to
Subsequently, this manufacturing method which comprises forming a hydantoin group by cyclization condensation at 50-160 degreeC.
20． A moisture curable composition comprising the polyurethane prepolymer of item 1 above.

Claims (3)

式(I) ：
Figure 0003866370
（ここで、Ａは、ＮＣＯ含有量を０．４〜５％有するイソシアネートプレポリマーからＮＣＯ基を除いて得られる基を示し、Ｒは、線状または分岐状の炭素原子数１〜８のアルキル基を示し、Ｘ、ＹおよびＺは、同一または異なり、炭素原子数１〜４のアルキルまたはアルコキシ基であって、かつ少なくとも１個の基はアルコキシ基であり、ｎは平均値で１．５〜４である）
に相当する、アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマー。Formula (I):
Figure 0003866370
 (Here, A represents a group obtained by removing an NCO group from an isocyanate prepolymer having an NCO content of 0.4 to 5%, and R represents a linear or branched alkyl having 1 to 8 carbon atoms. X, Y and Z are the same or different and are an alkyl or alkoxy group having 1 to 4 carbon atoms, and at least one group is an alkoxy group, and n is an average value of 1.5 ~ 4)
A polyurethane prepolymer having an alkoxysilane group and a hydantoin group. アルコキシシラン基およびヒダントイン基を有するポリウレタンプレポリマーの製造方法であって、
i) ＮＣＯ含有量を０．４〜５％有し、平均官能価が１．５〜４のイソシアネ
ートプレポリマーと
ii) 式(II)：
Figure 0003866370
（ここで、Ｒは線状または分岐状の炭素原子数１〜８アルキル基を示し、Ｘ、ＹおよびＺは、同一または異なり、アルキルまたはアルコキシ基であり、かつ少なくとも一個の基はアルコキシ基である）
に相当するアミノアルコキシシランとを反応させ、次いで、５０〜１６０℃で環化縮合してヒダントイン基を形成することからなる該製造方法。A method for producing a polyurethane prepolymer having an alkoxysilane group and a hydantoin group,
i) an isocyanate prepolymer having an NCO content of 0.4-5% and an average functionality of 1.5-4;
ii) Formula (II):
Figure 0003866370
 (Wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms, X, Y and Z are the same or different, and are an alkyl or alkoxy group, and at least one group is an alkoxy group. is there)
And then producing a hydantoin group by cyclization condensation at 50 to 160 ° C. 請求項１のポリウレタンプレポリマーを含有する湿分硬化性組成物。A moisture curable composition comprising the polyurethane prepolymer of claim 1.
JP13743597A 1996-05-15 1997-05-13 Polyurethane prepolymers having alkoxysilane groups and hydantoin groups and their use in the production of sealants Expired - Fee Related JP3866370B2 (en)

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